Combination of active substances with insecticidal properties

ABSTRACT

The invention relates to novel insecticidal active compound combinations comprising, firstly, compounds which act as insecticides on nicotinergic acetylcholine receptors as agonists and antagonists, and at least one active compound from the group of the anthranilamides, which combinations are suitable for protecting plants against attack by pests.

This application is a 35 U.S.C. §371 U.S. National Phase filing ofInternational Application No. PCT/EP 2004/012328, filed Oct. 30, 2004,which claims the benefit of German Patent Application No. 103 53 278.1,filed Nov. 14, 2003 and of German Patent Application No. 10 2004 006075.4, filed Feb. 7, 2004.

The present invention relates to novel active compound combinationscomprising, firstly, known compounds which act as insecticides onnicotinergic acetylcholine receptors as agonists and antagonists and,secondly, further known insecticidally active compounds, whichcombinations are highly suitable for the broad control of animal pests,such as insects.

It is already known that certain agonists and antagonists of thenicotinergic acetylcholine receptor have insecticidal properties. Theactivity of these compounds is good; however, at low application ratesor with respect to the activity spectrum, they are sometimesunsatisfactory.

The agonists and antagonists of the nicotinergic acetylcholine receptorsare known compounds, which are known from the following publications:

European Published Specifications Nos. 0 464 830, 0 428 941, 0 425 978,0 386 565, 0 383 091, 0 375 907, 0 364 844, 0 315 826, 0 259 738, 0 254859, 0 235 725, 0 212 600, 0 192 060, 0 163 855, 0 154 178, 0 136 636, 0136 686, 0 303 570, 0 302 833, 0 306 696, 0 189 972, 0 455 000, 0 135956, 0 471 372, 0 302 389, 0 428 941, 0 376 279, 0 493 369, 0 580 553, 0649 845, 0 685 477, 0 483 055, 0 580 553; German PublishedSpecifications Nos. 36 39 877, 37 12 307; Japanese PublishedSpecifications Nos. 3-220176, 2-207083, 63-307857, 63-287764, 3-246283,4-9371, 3-279359, 3-255072, 5-178833, 7-173157, 8-291171; U.S. Pat. Nos.5,034,524; 4,948,798; 4,918,086; 5,039,686; 5,034,404; 5,532,365; PCTapplications Nos. WO 91/17 659, 91/4965; French application No. 2 611114; Brazilian application No. 88 03 621.

The generic formulae and definitions described in these publications andthe individual compounds described therein are expressly incorporatedherein by way of reference.

To a certain extent, these compounds are summarized under the termnitromethylenes, nitroimines and related compounds.

Furthermore, it is already known that numerous heterocycles, organotincompounds, benzoylureas and pyrethroids have insecticidal and acaricidalproperties (cf. WO 93/22297, WO 93/10083, DE-A 26 41 343, EP-A 347 488,EP-A 210 487, U.S. Pat. No. 3,364,177 and EP-A 234 045). However, theactivity of these compounds is likewise not always satisfactory.

It has now been found that mixtures of compounds of the nicotinergicacetylcholine receptor agonists and antagonists of the formula (I)

in which

-   R represents hydrogen, optionally substituted radicals acyl, alkyl,    aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl;-   A represents a monofunctional group from the group consisting of    hydrogen, acyl, alkyl, aryl or represents a bifunctional group    attached to the radical Z;-   E represents an electron-withdrawing radical;-   X represents the radicals —CH═ or ═N—, where the radical —CH═ may be    attached to the radical Z′ instead of an H atom;-   Z represents a monofunctional group from the group consisting of    alkyl, —OR, —SR, —N(R)₂, where the radicals R are identical or    different and are as defined above, or represents a bifunctional    group attached to the radical A or the radical X,    and at least one active compound from the group of the    anthranilamides of the formula (II) are synergistically effective    and suitable for controlling animal pests.

Depending inter alia on the nature of the substituents, the compounds ofthe formula (I) may be present as geometrical and/or optical isomers orisomer mixtures of varying composition which, if appropriate, may beseparated in a customary manner. The present invention provides both thepure isomers and the isomer mixtures, their preparation and use and alsocompositions comprising them. However, hereinbelow, for the sake ofsimplicity, only compounds of the formula (I) are referred to, althoughwhat is meant are both the pure compounds and, if appropriate, alsomixtures having varying proportions of isomeric compounds.

Preference is given to active compound combinations comprising compoundsof the formula (I) in which the radicals are as defined below:

-   R represents hydrogen and also optionally substituted radicals from    the group consisting of acyl, alkyl, aryl, aralkyl,    heterocyclylalkyl, heteroaryl, heteroarylalkyl.    -   Acyl radicals which may be mentioned are formyl, alkylcarbonyl,        arylcarbonyl, alkylsulfonyl, arylsulfonyl,        (alkyl)(aryl)phosphoryl, which for their part may be        substituted, where aryl and alkyl have the preferred meanings        given below.    -   Alkyl which may be mentioned is C₁-C₁₀-alkyl, in particular        C₁-C₄-alkyl, specifically methyl, ethyl, isopropyl, sec- or        tert-butyl, which for their part may be substituted.    -   Aryl which may be mentioned are phenyl, naphthyl, in particular        phenyl.    -   Aralkyl which may be mentioned are phenylmethyl, phenethyl.    -   Heterocyclylalkyl which may be mentioned is the radical

-   -   Heteroaryl which may be mentioned is heteroaryl having up to 10        ring atoms and N, O, S, in particular N, as heteroatoms.        Specific mention may be made of thienyl, furyl, thiazolyl,        imidazolyl, pyridyl, benzothiazolyl, pyridazinyl.    -   Heteroarylalkyl which may be mentioned are heteroarylmethyl,        heteroarylethyl having up to 6 ring atoms and N, O, S, in        particular N, as heteroatoms, in particular optionally        substituted heteroaryl, as defined under heteroaryl.    -   Substituents which may be mentioned by way of example and by way        of preference are: alkyl having preferably 1 to 4, in particular        1 or 2, carbon atoms, such as methyl, ethyl, n- and isopropyl        and n-, iso- and tert-butyl; alkoxy having preferably 1 to 4, in        particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n- and        isopropyloxy and n-, iso- and tert-butyloxy; alkylthio having        preferably 1 to 4, in particular 1 or 2, carbon atoms, such as        methylthio, ethylthio, n- and isopropylthio and n-, iso- and        tert-butylthio; haloalkyl having preferably 1 to 4, in        particular 1 or 2, carbon atoms and preferably 1 to 5, in        particular 1 to 3, halogen atoms, where the halogen atoms are        identical or different and preferably represent fluorine,        chlorine or bromine, in particular fluorine, such as        trifluoromethyl, hydroxyl; halogen, preferably fluorine,        chlorine, bromine and iodine, in particular fluorine, chlorine        and bromine, cyano; nitro; amino; monoalkyl- and dialkylamino        having preferably 1 to 4, in particular 1 or 2, carbon atoms per        alkyl group, such as methylamino, methyl-ethylamino, n- and        isopropylamino and methyl-n-butylamino; carboxyl; carbalkoxy        having preferably 2 to 4, in particular 2 or 3, carbon atoms,        such as carbomethoxy and carboethoxy; sulfo (—SO₃H);        alkylsulfonyl having preferably 1 to 4, in particular 1 or 2,        carbon atoms, such as methylsulfonyl and ethylsulfonyl;        arylsulfonyl having preferably 6 or 10 arylcarbon atoms, such as        phenylsulfonyl, and also heteroarylamino and        heteroarylalkylamino, such as chloropyridylamino and        chloropyridylmethylamino.

-   A represents hydrogen or represents an optionally substituted    radical from the group consisting of acyl, alkyl, aryl, which,    preferably, have the meanings mentioned under R; A furthermore    represents a biofunctional group. Mention may be made of optionally    substituted alkylene having 1 to 4, in particular 1 to 2, C atoms,    substituents that may be mentioned being the substituents listed    further above (and where the alkylene groups may be interrupted by    heteroatoms from the group consisting of N, O, S).

-   A and Z together with the atoms to which they are attached may form    a saturated or unsaturated heterocyclic ring. The heterocyclic ring    may contain a further 1 or 2 identical or different heteroatoms    and/or hetero groups. Preferred heteroatoms are oxygen, sulfur or    nitrogen, and a preferred hetero group is N-alkyl, where the alkyl    of the N-alkyl group preferably contains 1 to 4, in particular 1 or    2, carbon atoms. Alkyl which may be mentioned are methyl, ethyl, n-    and isopropyl and n-, iso- and tert-butyl. The heterocyclic ring    contains 5 to 7, preferably 5 or 6, ring members.

Examples which may be mentioned of the compounds of the formula (I) inwhich A and Z together with the atoms to which they are attached form aring, are the following:

in which

-   R, E and X have the meanings given above and further below.-   E represents an electron-withdrawing radical, where particular    mention may be made of NO₂, CN, haloalkylcarbonyl, such as    halo-C₁-C₄-alkylcarbonyl, for example COCF₃, alkylsulfonyl (for    example SO₂—CH₃), haloalkylsulfonyl (for example SO₂CF₃) and very    particularly NO₂ or CN.-   X represents —CH═ or —N═.-   Z represents an optionally substituted radical from the group    consisting of alkyl, —OR, —SR, —NRR, where R and the substituents    preferably have the meanings indicated above.-   Z may, in addition to the ring mentioned above, together with the    atom to which it is attached and the radical

-   -   instead of X, form a saturated or unsaturated heterocyclic ring.        The heterocyclic ring may contain a further 1 or 2 identical or        different heteroatoms and/or hetero groups. Preferred        heteroatoms are oxygen, sulfur or nitrogen, and a preferred        hetero group is N-alkyl, where the alkyl or N-alkyl group        preferably contains 1 to 4, preferably 1 or 2, carbon atoms.    -   Alkyl which may be mentioned are methyl, ethyl, n- and isopropyl        and n-, iso and tert-butyl. The heterocyclic ring contains 5 to        7, preferably 5 or 6, ring members. Examples of the heterocyclic        ring which may be mentioned are pyrrolidine, piperidine,        piperazine, hexamethyleneimine, morpholine and        N-methylpiperazine.

Particularly preferred active compound combinations comprise anagonist/antagonist of the nicotinergic acetylcholine receptors of theformula (I), in which

-   R represents

-   -   where    -   n represents 0, 1 or 2, preferably 1,    -   Subst. represents one of the substituents listed above, in        particular halogen, especially chlorine, and        A, Z, X and E are as defined above.

-   R represents especially

Specific mention may be made of the following compounds of the formula(I):

Very particular preference is given to active compound combinationscomprising an agonist/antagonist of the nicotinergic acetylcholinereceptors of the formulae below:

in particular of the formulae below

Very particular preference is given to active compound combinationscomprising the compounds of the formulae (Ia), (Ik).

Very particular preference is furthermore given to active compoundcombinations comprising the compounds of the formulae (Ie), (Ig), (Ih),(Ii), (Il), (Im).

The anthranilamides of the formula (II) are likewise known compoundswhich are known from the following publications or embraced by them:

-   WO 01/70671, WO 03/015518, WO 03/015519, WO 03/016284, WO 03/016282,    WO 03/016283, WO 03/024222, WO 03/062226.

The generic formulae and definitions described in these publications andthe individual compounds described therein are expressly incorporatedinto the present application by way of reference.

The anthranilamides can be summarized under the formula (II):

in which

-   A¹ and A² independently of one another represent oxygen or sulfur,-   X¹ represents N or CR¹⁰,-   R¹ represents hydrogen or represents in each case optionally mono-    or polysubstituted C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or    C₃-C₆-cycloalkyl, where the substituents independently of one    another may be selected from the group consisting of R⁶, halogen,    cyano, nitro, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkyl-sulfonyl, C₂-C₄-alkoxycarbonyl,    C₁-C₄-alkylamino, C₂-C₈-dialkylamino, C₃-C₆-cyclo-alkylamino,    (C₁-C₄-alkyl)C₃-C₆-Cycloalkylamino and R¹¹,-   R² represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,    C₂-C₈-dialkylamino, C₃-C₆-cycloalkylamino, C₂-C₆-alkoxycarbonyl or    C₂-C₆-alkylcarbonyl,-   R³ represents hydrogen, R¹¹ or represents in each case optionally    mono- or polysubstituted C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₃-C₆-Cycloalkyl, where the substituents independently of one    another may be selected from the group consisting of R⁶, halogen,    cyano, nitro, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-alkylthio, C₁-C₄-alkyl-sulfinyl, C₁-C₄-alkylsulfonyl,    C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylcarbonyl, C₃-C₆-trialkyl-silyl,    R¹¹, phenyl, phenoxy and a 5- or 6-membered heteroaromatic ring,    where each phenyl, phenoxy and 5- or 6-membered heteroaromatic ring    may optionally be substituted and where the substituents    independently of one another may be selected from one to three    radicals W or one or more radicals R¹², or-   R² and R³ may be attached to one another and form the ring M,-   R⁴ represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl,    C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl, halogen, cyano, nitro,    hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkylamino,    C₂-C₈-dialkylamino, C₃-C₆-cycloalkylamino, C₃-C₆-trialkylsilyl or    represents in each case optionally mono- or polysubstituted phenyl,    benzyl or phenoxy, where the substituents independently of one    another may be selected from the group consisting of C₁-C₄-alkyl,    C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl,    C₂-C₄-haloalkenyl, C₂-C₄-haloalkynyl, C₃-C₆-halocycloalkyl, halogen,    cyano, nitro, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-alkylamino,    C₂-C₈-dialkylamino, C₃-C₆-cycloalkylamino,    C₃-C₆-(alkyl)cycloalkylamino, C₂-C₄-alkylcarbonyl,    C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylaminocarbonyl,    C₃-C₈-dialkyl-aminocarbonyl and C₃-C₆-trialkylsilyl,-   R⁵ and R⁸ in each case independently of one another represent    hydrogen, halogen or represent in each case optionally substituted    C₁-C₄-alkyl, C₁-C₄-haloalkyl, R¹², G, J, —OJ, —OG, —S(O)_(p)-J,    —S(O)_(p)-G, —S(O)_(p)-phenyl, where the substituents independently    of one another may be selected from one to three radicals W or from    the group consisting of R¹², C₁-C₁₀-alkyl, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₁-C₄-alkoxy and C₁-C₄-alkythio, where each    substituent may be substituted by one or more substituents    independently of one another selected from the group consisting of    G, J, R⁶, halogen, cyano, nitro, amino, hydroxyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl,    C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl,    C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkylamino, C₂-C₈-dialkylamino,    C₃-C₆-trialkylsilyl, phenyl and phenoxy, where each phenyl or    phenoxy ring may optionally be substituted and where the    substituents independently of one another may be selected from one    to three radicals W or one or more radicals R¹²,-   G in each case independently of one another represent a 5- or    6-membered nonaromatic carbocyclic or heterocyclic ring which    optionally contains one or two ring members from the group    consisting of C(═O), SO and S(═O) and which may optionally be    substituted by one to four substituents independently of one another    selected from the group consisting of C₁-C₂-alkyl, halogen, cyano,    nitro and C₁-C₂-alkoxy, or independently of one another represent    C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₇-cycloalkyl,    (cyano)C₃-C₇-cycloalkyl, (C₁-C₄-alkyl)C₃-C₆-cycloalkyl,    (C₃-C₆-cycloalkyl)C₁-C₄-alkyl, where each cycloalkyl,    (alkyl)cycloalkyl and (cycloalkyl)alkyl may optionally be    substituted by one or more halogen atoms,-   J in each case independently of one another represent an optionally    substituted 5- or 6-membered heteroaromatic ring, where the    substituents independently of one another may be selected from one    to three radicals W or one or more radicals R¹²,-   R⁶ independently of one another represent —C(=E¹)R¹⁹, -LC(=E¹)R¹⁹,    —C(=E¹)LR¹⁹, -LC(=E¹)LR¹⁹, —OP(=Q)(OR¹⁹)₂, —SO₂LR¹⁸ or -LSO₂LR¹⁹,    where each E¹ independently of the others represents O, S, N—R¹⁵,    N—OR¹⁵, N—N(R¹⁵)₂, N—S═O, N—CN or N—NO₂,-   R⁷ represents hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, halogen,    C₁-C₄-alkoxy, C₁-C₄-halo-alkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl,-   R⁹ represents C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy,    C₁-C₄-haloalkylsulfinyl or halogen,-   R¹⁰ represents hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, halogen,    cyano or C₁-C₄-haloalkoxy,-   R¹¹ in each case independently of one another represent in each case    optionally mono-to trisubstituted C₁-C₆-alkylthio,    C₁-C₆-alkylsulfenyl, C₁-C₆-haloalkythio, C₁-C₆-haloalkyl-sulfenyl,    phenylthio or phenylsulfenyl, where the substituents independently    of one another may be selected from the list consisting of W,    —S(O)_(n)N(R¹⁶)₂, —C(═O)R¹³, -L(C═O)R¹⁴, —S(C═O)LR¹⁴, —C(═O)LR¹³,    —S(O)_(n)N¹³C(═O)R¹³, —S(O)_(n)NR¹³C(═O)LR¹⁴ and    —S(O)_(n)NR¹³S(O)₂LR¹⁴,-   L in each case independently of one another represent O, NR¹⁸ or S,-   R¹² in each case independently of one another represent —B(OR¹⁷⁾ ₂,    amino, SH, thiocyanato, C₃-C₈-trialkylsilyloxy, C₁-C₄-alkyl    disulfide, —SF₅, —C(=E¹)R¹⁹, -LC(=E¹)R¹⁹, —C(=E¹)LR¹⁹, -LC(=E¹)LR¹⁹,    —OP(=Q)(OR¹⁹)₂, —SO₂LR¹⁹ or -LSO₂LR¹⁹,-   Q represents O or S,-   R¹³ in each case independently of one another represent hydrogen or    represent in each case optionally mono- or polysubstituted    C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₃-C₆-cycloalkyl, where    the substituents independently of one another may be selected from    the group consisting of R⁶, halogen, cyano, nitro, hydroxyl,    C₁-C₄-alkoxy, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl,    C₁-C₄-alkylamino, C₂-C₈-dialkylamino, C₃-C₆-cycloalkylamino and    (C₁-C₄-alkyl)C₃-C₆-cycloalkylamino,-   R¹⁴ in each case independently of one another represent in each case    mono- or polysubstituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,    C₂-C₂₀-alkynyl or C₃-C₆-cycloalkyl, where the substituents    independently of one another may be selected from the group    consisting of R⁶, halogen, cyano, nitro, hydroxyl, C₁-C₄-alkoxy,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-alkyl-amino,    C₂-C₈-dialkylamino, C₃-C₆-cycloalkylamino and    (C₁-C₄-alkyl)C₃-C₆-cycloalkyl-amino or represent optionally    substituted phenyl, where the substituents independently of one    another may be selected from one to three radicals W or one or more    radicals R¹²,-   R¹⁵ in each case independently of one another represent hydrogen or    represent in each case mono- or polysubstituted C₁-C₆-haloalkyl or    C₁-C₆-alkyl, where the substituents independently of one another may    be selected from the group consisting of cyano, nitro, hydroxyl,    C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkylamino,    C₂-C₈-dialkylamino, C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylcarbonyl,    C₃-C₆-trialkylsilyl and optionally substituted phenyl, where the    substituents independently of one another may be selected from one    to three radicals W or one or more radicals R¹², or N(R¹⁵)₂    represents a cycle which forms the ring M,-   R¹⁶ represents C₁-C₁₂-alkyl or C₁-C₁₂-haloalkyl, or N(R¹⁶)₂    represents a cycle which forms the ring M,-   R¹⁷ in each case independently of one another represent hydrogen or    C₁-C₄-alkyl, or B(OR¹⁷)₂ represents a ring, where the two oxygen    atoms are attached via a chain to two or three carbon atoms which    are optionally substituted by one or two substituents independently    of one another selected from the group consisting of methyl and    C₂-C₆-alkoxycarbonyl,-   R¹⁸ in each case independently of one another represent hydrogen,    C₁-C₆-alkyl or C₁-C₆-haloalkyl, or N(R¹³)(R¹⁸) represents a cycle    which forms the ring M,-   R¹⁹ in each case independently of one another represent hydrogen or    represent in each case optionally mono- or polysubstituted    C₁-C₆-alkyl, where the substituents independently of one another may    be selected from the group consisting of cyano, nitro, hydroxyl,    C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkylamino,    C₂-C₈-dialkylamino, CO₂H, C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylcarbonyl,    C₃-C₆-trialkylsilyl and optionally substituted phenyl, where the    substituents independently of one another may be selected from one    to three radicals W, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl or phenyl or    pyridyl, each of which is optionally mono- to trisubstituted by W,-   M in each case represents an optionally mono- to tetrasubstituted    ring which, in addition to the nitrogen atom which is attached to    the substituent pair R¹³ and R¹⁸, (R¹⁵)₂ or (R¹⁶)₂, contains two to    six carbon atoms and optionally additionally a further nitrogen,    sulfur or oxygen atom, and where the substituents independently of    one another may be selected from the group consisting of    C₁-C₂-alkyl, halogen, cyano, nitro and C₁-C₂-alkoxy,-   W in each case independently of one another represent C₁-C₄-alkyl,    C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl,    C₂-C₄-haloalkenyl, C₂-C₄-haloalkynyl, C₃-C₆-halocycloalkyl, halogen,    cyano, nitro, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-alkylamino,    C₂-C₈-dialkylamino, C₃-C₆-cycloalkylamino,    (C₁-C₄-alkyl)C₃-C₆-cycloalkylamino, C₂-C₄-alkylcarbonyl,    C₂-C₆-alkoxy-carbonyl, CO₂H, C₂-C₆-alkylaminocarbonyl,    C₃-C₈-dialkylaminocarbonyl or C₃-C₆-trialkylsilyl,-   n in each case independently of one another represent 0 or 1,-   p in each case independently of one another represent 0, 1 or 2.

If (a) R⁵ represents hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₁-C₄-haloalkoxy,C₁-C₄-haloalkylthio or halogen and (b) R⁸ represents hydrogen,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, halogen, C₂-C₄-alkylcarbonyl,C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylaminocarbonyl or C₃-C₈dialkyl-aminocarbonyl, (c) at least one substituent selected from thegroup consisting of R⁶, R¹¹ and R¹² is present and (d), if R¹² is notpresent, at least one R⁶ or R¹¹ is different from C₂-C₆-alkylcarbonyl,C₂-C₆ alkoxycarbonyl, C₂-C₆-alkylaminocarbonyl andC₃-C₈-dialkylaminocarbonyl.

The compounds of the general formula (II) include N-oxides and salts.

Depending inter alia on the nature of the substituents, the compounds ofthe formula (II) may be present as geometrical and/or optical isomers orisomer mixtures of varying composition which, if appropriate, may beseparated in a customary manner. The present invention provides both thepure isomers and the isomer mixtures, their preparation and use and alsocompositions comprising them. However, hereinbelow, for the sake ofsimplicity, only compounds of the formula (II) are referred to, althoughwhat is meant are both the pure compounds and, if appropriate, alsomixtures having varying proportions of isomeric compounds.

Preference is given to active compound combinations comprising compoundsof the formula (II-1)

in which

-   R² represents hydrogen or C₁-C₆-alkyl,-   R³ represents C₁-C₆-alkyl which is optionally substituted by a    radical R⁶,-   R⁴ represents C₁-C₄-alkyl, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy or    halogen,-   R⁵ represents hydrogen, C₁-C₄-alkyl, C₁-C₂-haloalkyl,    C₁-C₂-haloalkoxy or halogen,-   R⁶ represents —C(=E²)R¹⁹, -LC(=E²)R¹⁹, —C(=E²)LR¹⁹ or -LC(=E²)LR¹⁹,    where each E² independently of the others represents O, S, N—R⁵,    N—OR¹⁵, N—N(R¹⁵)₂, and each L independently of the others represents    O or NR¹⁸,-   R⁷ represents C₁-C₄-haloalkyl or halogen,-   R⁹ represents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy,    S(O)_(p)C₁-C₂-haloalkyl or halogen,-   R¹⁵ in each case independently of one another represent hydrogen or    represent in each case optionally substituted C₁-C₆-haloalkyl or    C₁-C₆-alkyl, where the substituents independently of one another may    be selected from the group consisting of cyano, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl,    C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl or    C₁-C₄-haloalkylsulfonyl,-   R¹⁸ in each case represents hydrogen or C₁-C₄-alkyl,-   R¹⁹ in each case independently of one another represent hydrogen or    C₁-C₆-alkyl,-   p independently of one another represents 0, 1, 2.

In the radical definitions mentioned as being preferred, halogenrepresents fluorine, chlorine, bromine and iodine, in particularfluorine, chlorine and bromine.

Particular preference is given to active compound combinationscomprising compounds of the formula (II-1), in which

-   R² represents hydrogen or methyl,-   R³ represents C₁-C₄-alkyl (in particular methyl, ethyl, n-,    isopropyl, n-, iso-, sec-, tert-butyl),-   R⁴ represents methyl, trifluoromethyl, trifluoromethoxy, fluorine,    chlorine, bromine or iodine,-   R⁵ represents hydrogen, fluorine, chlorine, bromine, iodine,    trifluoromethyl or trifluoromethoxy,-   R⁷ represents chlorine or bromine,-   R⁹ represents trifluoromethyl, chlorine, bromine, difluoromethoxy or    trifluoroethoxy.

Very particular preference is given to active compound combinationscomprising the following compounds of the formula (II-1):

(II-1)

Example No. R² R³ R⁴ R⁵ R⁷ R⁹ m. p. (° C.) II-1-1 H Me Me Cl Cl CF₃185-186 II-1-2 H Me Me Cl Cl OCH₂CF₃ 207-208 II-1-3 H Me Me Cl Cl Cl225-226 II-1-4 H Me Me Cl Cl Br 162-164 II-1-5 H Me Cl Cl Cl CF₃ 155-157II-1-6 H Me Cl Cl Cl OCH₂CF₃ 192-195 II-1-7 H Me Cl Cl Cl Cl 205-206II-1-8 H Me Cl Cl Cl Br 245-246 II-1-9 H i-Pr Me Cl Cl CF₃ 195-196II-1-10 H i-Pr Me Cl Cl OCH₂CF₃ 217-218 II-1-11 H i-Pr Me Cl Cl Cl173-175 II-1-12 H i-Pr Me Cl Cl Br 159-161 II-1-13 H i-Pr Cl Cl Cl CF₃200-201 II-1-14 H i-Pr Cl Cl Cl OCH₂CF₃ 232-235 II-1-15 H i-Pr Cl Cl ClCl 197-199 II-1-16 H i-Pr Cl Cl Cl Br 188-190 II-1-17 H Et Me Cl Cl CF₃163-164 II-1-18 H Et Me Cl Cl OCH₂CF₃ 205-207 II-1-19 H Et Me Cl Cl Cl199-200 II-1-20 H Et Me Cl Cl Br 194-195 II-1-21 H Et Cl Cl Cl CF₃201-202 II-1-22 H Et Cl Cl Cl Cl 206-208 II-1-23 H Et Cl Cl Cl Br214-215 II-1-24 H t-Bu Me Cl Cl CF₃ 223-225 II-1-25 H t-Bu Me Cl Cl Cl163-165 II-1-26 H t-Bu Me Cl Cl Br 159-161 II-1-27 H t-Bu Cl Cl Cl CF₃170-172 II-1-28 H t-Bu Cl Cl Cl Cl 172-173 II-1-29 H t-Bu Cl Cl Cl Br179-180 II-1-30 H Me Me Br Cl CF₃ 222-223 II-1-31 H Et Me Br Cl CF₃192-193 II-1-32 H i-Pr Me Br Cl CF₃ 197-198 II-1-33 H t-Bu Me Br Cl CF₃247-248 II-1-34 H Me Me Br Cl Cl 140-141 II-1-35 H Et Me Br Cl Cl192-194 II-1-36 H i-Pr Me Br Cl Cl 152-153 II-1-37 H t-Bu Me Br Cl Cl224-225 II-1-38 H Me Me Br Cl Br 147-149 II-1-39 H Et Me Br Cl Br194-196 II-1-40 H i-Pr Me Br Cl Br 185-187 II-1-41 H t-Bu Me Br Cl Br215-221 II-1-42 H Me Me I Cl CF₃ 199-200 II-1-43 H Et Me I Cl CF₃199-200 II-1-44 H i-Pr Me I Cl CF₃ 188-189 II-1-45 H t-Bu Me I Cl CF₃242-243 II-1-46 H Me Me I Cl Cl 233-234 II-1-47 H Et Me I Cl Cl 196-197II-1-48 H i-Pr Me I Cl Cl 189-190 II-1-49 H t-Bu Me I Cl Cl 228-229II-1-50 H Me Me I Cl Br 229-230 II-1-51 H iPr Me I Cl Br 191-192 II-1-52H Me Br Br Cl CF₃ 162-163 II-1-53 H Et Br Br Cl CF₃ 188-189 II-1-54 Hi-Pr Br Br Cl CF₃ 192-193 II-1-55 H t-Bu Br Br Cl CF₃ 246-247 II-1-56 HMe Br Br Cl Cl 188-190 II-1-57 H Et Br Br Cl Cl 192-194 II-1-58 H i-PrBr Br Cl Cl 197-i99 II-1-59 H t-Bu Br Br Cl Cl 210-212 II-1-60 H Me BrBr Cl Br 166-168 II-1-61 H Et Br Br Cl Br 196-197 II-1-62 H i-Pr Br BrCl Br 162-163 II-1-63 H t-Bu Br Br Cl Br 194-196 II-1-64 H t-Bu Cl Br ClCF₃ 143-145 II-1-65 Me Me Br Br Cl Cl 153-155 II-1-66 Me Me Me Br Cl CF₃207-208 II-1-67 Me Me Cl Cl Cl Cl 231-232 II-1-68 Me Me Br Br Cl Br189-190 II-1-69 Me Me Cl Cl Cl Br 216-218 II-1-70 Me Me Cl Cl Cl CF₃225-227 II-1-71 Me Me Br Br Cl CF₃ 228-229 II-1-72 H i-Pr Me H Cl CF₃237-239

Especially preferred are active compound combinations comprising acompound of the formulae below

Emphasis is given to the following specifically mentioned activecompound combinations (2-compound mixtures) comprising a compound of theformula (I) and a compound of the formula (II-1):

Active compound No. combination comprising  1a) (Ia) and (II-1-1)  1b)(Ie) and (II-1-1)  1c) (Ig) and (II-1-1)  1d) (Ih) and (II-1-1)  1e)(Ii) and (II-1-1)  1f) (Ik) and (II-1-1)  1g) (Il) and (II-1-1)  1h)(Im) and (II-1-1)  2a) (Ia) and (II-1-2)  2b) (Ie) and (II-1-2)  2c)(Ig) and (II-1-2)  2d) (Ih) and (II-1-2)  2e) (Ii) and (II-1-2)  2f)(Ik) and (II-1-2)  2g) (Il) and (II-1-2)  2h) (Im) and (II-1-2)  3a)(Ia) and (II-1-3)  3b) (Ie) and (II-1-3)  3c) (Ig) and (II-1-3)  3d)(Ih) and (II-1-3)  3e) (Ii) and (II-1-3)  3f) (Ik) and (II-1-3)  3g)(Il) and (II-1-3)  3h) (Im) and (II-1-3)  4a) (Ia) and (II-1-4)  4b)(Ie) and (II-1-4)  4c) (Ig) and (II-1-4)  4d) (Ih) and (II-1-4)  4e)(Ii) and (II-1-4)  4f) (Ik) and (II-1-4)  4g) (Il) and (II-1-4)  4h)(Im) and (II-1-4)  5a) (Ia) and (II-1-5)  5b) (Ie) and (II-1-5)  5c)(Ig) and (II-1-5)  5d) (Ih) and (II-1-5)  5e) (Ii) and (II-1-5)  5f)(Ik) and (II-1-5)  5g) (Il) and (II-1-5)  5h) (Im) and (II-1-5)  6a)(Ia) and (II-1-6)  6b) (Ie) and (II-1-6)  6c) (Ig) and (II-1-6)  6d)(Ih) and (II-1-6)  6e) (Ii) and (II-1-6)  6f) (Ik) and (II-1-6)  6g)(Il) and (II-1-6)  6h) (Im) and (II-1-6)  7a) (Ia) and (II-1-7)  7b)(Ie) and (II-1-7)  7c) (Ig) and (II-1-7)  7d) (Ih) and (II-1-7)  7e)(Ii) and (II-1-7)  7f) (Ik) and (II-1-7)  7g) (Il) and (II-1-7)  7h)(Im) and (II-1-7)  8a) (Ia) and (II-1-8)  8b) (Ie) and (II-1-8)  8c)(Ig) and (II-1-8)  8d) (Ih) and (II-1-8)  8e) (Ii) and (II-1-8)  8f)(Ik) and (II-1-8)  8g) (Il) and (II-1-8)  8h) (Im) and (II-1-8)  9a)(Ia) and (II-1-9)  9b) (Ie) and (II-1-9)  9c) (Ig) and (II-1-9)  9d)(Ih) and (II-1-9)  9e) (Ii) and (II-1-9)  9f) (Ik) and (II-1-9)  9g)(Il) and (II-1-9)  9h) (Im) and (II-1-9) 10a) (Ia) and (II-1-11) 10b)(Ie) and (II-1-11) 10c) (Ig) and (II-1-11) 10d) (Ih) and (II-1-11) 10e)(Ii) and (II-1-11) 10f) (Ik) and (II-1-11) 10g) (Il) and (II-1-11) 10h)(Im) and (II-1-11) 11a) (Ia) and (II-1-12) 11b) (Ie) and (II-1-12) 11c)(Ig) and (II-1-12) 11d) (Ih) and (II-1-12) 11e) (Ii) and (II-1-12) 11f)(Ik) and (II-1-12) 11g) (Il) and (II-1-12) 11h) (Im) and (II-1-12) 12a)(Ia) and (II-1-13) 12b) (Ie) and (II-1-13) 12c) (Ig) and (II-1-13) 12d)(Ih) and (II-1-13) 12e) (Ii) and (II-1-13) 12f) (Ik) and (II-1-13) 12g)(Il) and (II-1-13) 12h) (Im) and (II-1-13) 13a) (Ia) and (II-1-15) 13b)(Ie) and (II-1-15) 13c) (Ig) and (II-1-15) 13d) (Ih) and (II-1-15) 13e)(Ii) and (II-1-15) 13f) (Ik) and (II-1-15) 13g) (Il) and (II-1-15) 13h)(Im) and (II-1-15) 14a) (Ia) and (II-1-16) 14b) (Ie) and (II-1-16) 14c)(Ig) and (II-1-16) 14d) (Ih) and (II-1-16) 14e) (Ii) and (II-1-16) 14f)(Ik) and (II-1-16) 14g) (Il) and (II-1-16) 14h) (Im) and (II-1-16) 15a)(Ia) and (II-1-19) 15b) (Ie) and (II-1-19) 15c) (Ig) and (II-1-19) 15d)(Ih) and (II-1-19) 15e) (Ii) and (II-1-19) 15f) (Ik) and (II-1-19) 15g)(Il) and (II-1-19) 15h) (Im) and (II-1-19) 16a) (Ia) and (II-1-21) 16b)(Ie) and (II-1-21) 16c) (Ig) and (II-1-21) 16d) (Ih) and (II-1-21) 16e)(Ii) and (II-1-21) 16f) (Ik) and (II-1-21) 16g) (Il) and (II-1-21) 16h)(Im) and (II-1-21) 17a) (Ia) and (II-1-22) 17b) (Ie) and (II-1-22) 17c)(Ig) and (II-1-22) 17d) (Ih) and (II-1-22) 17e) (Ii) and (II-1-22) 17f)(Ik) and (II-1-22) 17g) (Il) and (II-1-22) 17h) (Im) and (II-1-22) 18a)(Ia) and (II-1-23) 18b) (Ie) and (II-1-23) 18c) (Ig) and (II-1-23) 18d)(Ih) and (II-1-23) 18e) (Ii) and (II-1-23) 18f) (Ik) and (II-1-23) 18g)(Il) and (II-1-23) 18h) (Im) and (II-1-23) 19a) (Ia) and (II-1-24) 19b)(Ie) and (II-1-24) 19c) (Ig) and (II-1-24) 19d) (Ih) and (II-1-24) 19e)(Ii) and (II-1-24) 19f) (Ik) and (II-1-24) 19g) (Il) and (II-1-24) 19h)(Im) and (II-1-24) 20a) (Ia) and (II-1-26) 20b) (Ie) and (II-1-26) 20c)(Ig) and (II-1-26) 20d) (Ih) and (II-1-26) 20e) (Ii) and (II-1-26) 20f)(Ik) and (II-1-26) 20g) (Il) and (II-1-26) 20h) (Im) and (II-1-26) 21a)(Ia) and (II-1-27) 21b) (Ie) and (II-1-27) 21c) (Ig) and (II-1-27) 21d)(Ih) and (II-1-27) 21e) (Ii) and (II-1-27) 21f) (Ik) and (II-1-27) 21g)(Il) and (II-1-27) 21h) (Im) and (II-1-27) 22a) (Ia) and (II-1-29) 22b)(Ie) and (II-1-29) 22c) (Ig) and (II-1-29) 22d) (Ih) and (II-1-29) 22e)(Ii) and (II-1-29) 22f) (Ik) and (II-1-29) 22g) (Il) and (II-1-29) 22h)(Im) and (II-1-29) 23a) (Ia) and (II-1-30) 23b) (Ie) and (II-1-30) 23c)(Ig) and (II-1-30) 23d) (Ih) and (II-1-30) 23e) (Ii) and (II-1-30) 23f)(Ik) and (II-1-30) 23g) (Il) and (II-1-30) 23h) (Im) and (II-1-30) 24a)(Ia) and (II-1-31) 24b) (Ie) and (II-1-31) 24c) (Ig) and (II-1-31) 24d)(Ih) and (II-1-31) 24e) (Ii) and (II-1-31) 24f) (Ik) and (II-1-31) 24g)(Il) and (II-1-31) 24h) (Im) and (II-1-31) 25a) (Ia) and (II-1-32) 25b)(Ie) and (II-1-32) 25c) (Ig) and (II-1-32) 25d) (Ih) and (II-1-32) 25e)(Ii) and (II-1-32) 25f) (Ik) and (II-1-32) 25g) (Il) and (II-1-32) 25h)(Im) and (II-1-32) 26a) (Ia) and (II-1-33) 26b) (Ie) and (II-1-33) 26c)(Ig) and (II-1-33) 26d) (Ih) and (II-1-33) 26e) (Ii) and (II-1-33) 26f)(Ik) and (II-1-33) 26g) (Il) and (II-1-33) 26h) (Im) and (II-1-33) 27a)(Ia) and (II-1-38) 27b) (Ie) and (II-1-38) 27c) (Ig) and (II-1-38) 27d)(Ih) and (II-1-38) 27e) (Ii) and (II-1-38) 27f) (Ik) and (II-1-38) 27g)(Il) and (II-1-38) 27h) (Im) and (II-1-38) 28a) (Ia) and (II-1-39) 28b)(Ie) and (II-1-39) 28c) (Ig) and (II-1-39) 28d) (Ih) and (II-1-39) 28e)(Ii) and (II-1-39) 28f) (Ik) and (II-1-39) 28g) (Il) and (II-1-39) 28h)(Im) and (II-1-39) 29a) (Ia) and (II-1-40) 29b) (Ie) and (II-1-40) 29c)(Ig) and (II-1-40) 29d) (Ih) and (II-1-40) 29e) (Ii) and (II-1-40) 29f)(Ik) and (II-1-40) 29g) (Il) and (II-1-40) 29h) (Im) and (II-1-40) 30a)(Ia) and (II-1-42) 30b) (Ie) and (II-1-42) 30c) (Ig) and (II-1-42) 30d)(Ih) and (II-1-42) 30e) (Ii) and (II-1-42) 30f) (Ik) and (II-1-42) 30g)(Il) and (II-1-42) 30h) (Im) and (II-1-42) 31a) (Ia) and (II-1-43) 31b)(Ie) and (II-1-43) 31c) (Ig) and (II-1-43) 31d) (Ih) and (II-1-43) 31e)(Ii) and (II-1-43) 31f) (Ik) and (II-1-43) 31g) (Il) and (II-1-43) 31h)(Im) and (II-1-43) 32a) (Ia) and (II-1-44) 32b) (Ie) and (II-1-44) 32c)(Ig) and (II-1-44) 32d) (Ih) and (II-1-44) 32e) (Ii) and (II-1-44) 32f)(Ik) and (II-1-44) 32g) (Il) and (II-1-44) 32h) (Im) and (II-1-44) 33a)(Ia) and (II-1-50) 33b) (Ie) and (II-1-50) 33c) (Ig) and (II-1-50) 33d)(Ih) and (II-1-50) 33e) (Ii) and (II-1-50) 33f) (Ik) and (II-1-50) 33g)(Il) and (II-1-50) 33h) (Im) and (II-1-50) 34a) (Ia) and (II-1-51) 34b)(Ie) and (II-1-51) 34c) (Ig) and (II-1-51) 34d) (Ih) and (II-1-51) 34e)(Ii) and (II-1-51) 34f) (Ik) and (II-1-51) 34g) (Il) and (II-1-51) 34h)(Im) and (II-1-51) 35a) (Ia) and (II-1-52) 35b) (Ie) and (II-1-52) 35c)(Ig) and (II-1-52) 35d) (Ih) and (II-1-52) 35e) (Ii) and (II-1-52) 35f)(Ik) and (II-1-52) 35g) (Il) and (II-1-52) 35h) (Im) and (II-1-52) 36a)(Ia) and (II-1-53) 36b) (Ie) and (II-1-53) 36c) (Ig) and (II-1-53) 36d)(Ih) and (II-1-53) 36e) (Ii) and (II-1-53) 36f) (Ik) and (II-1-53) 36g)(Il) and (II-1-53) 36h) (Im) and (II-1-53) 37a) (Ia) and (II-1-54) 37b)(Ie) and (II-1-54) 37c) (Ig) and (II-1-54) 37d) (Ih) and (II-1-54) 37e)(Ii) and (II-1-54) 37f) (Ik) and (II-1-54) 37g) (Il) and (II-1-54) 37h)(Im) and (II-1-54) 38a) (Ia) and (II-1-55) 38b) (Ie) and (II-1-55) 38c)(Ig) and (II-1-55) 38d) (Ih) and (II-1-55) 38e) (Ii) and (II-1-55) 38f)(Ik) and (II-1-55) 38g) (Il) and (II-1-55) 38h) (Im) and (II-1-55) 39a)(Ia) and (II-1-56) 39b) (Ie) and (II-1-56) 39c) (Ig) and (II-1-56) 39d)(Ih) and (II-1-56) 39e) (Ii) and (II-1-56) 39f) (Ik) and (II-1-56) 39g)(Il) and (II-1-56) 39h) (Im) and (II-1-56) 40a) (Ia) and (II-1-57) 40b)(Ie) and (II-1-57) 40c) (Ig) and (II-1-57) 40d) (Ih) and (II-1-57) 40e)(Ii) and (II-1-57) 40f) (Ik) and (II-1-57) 40g) (Il) and (II-1-57) 40h)(Im) and (II-1-57) 41a) (Ia) and (II-1-58) 41b) (Ie) and (II-1-58) 41c)(Ig) and (II-1-58) 41d) (Ih) and (II-1-58) 41e) (Ii) and (II-1-58) 41f)(Ik) and (II-1-58) 41g) (Il) and (II-1-58) 41h) (Im) and (II-1-58) 42a)(Ia) and (II-1-60) 42b) (Ie) and (II-1-60) 42c) (Ig) and (II-1-60) 42d)(Ih) and (II-1-60) 42e) (Ii) and (II-1-60) 42f) (Ik) and (II-1-60) 42g)(Il) and (II-1-60) 42h) (Im) and (II-1-60) 43a) (Ia) and (II-1-61) 43b)(Ie) and (II-1-61) 43c) (Ig) and (II-1-61) 43d) (Ih) and (II-1-61) 43e)(Ii) and (II-1-61) 43f) (Ik) and (II-1-61) 43g) (Il) and (II-1-61) 43h)(Im) and (II-1-61) 44a) (Ia) and (II-1-62) 44b) (Ie) and (II-1-62) 44c)(Ig) and (II-1-62) 44d) (Ih) and (II-1-62) 44e) (Ii) and (II-1-62) 44f)(Ik) and (II-1-62) 44g) (Il) and (II-1-62) 44h) (Im) and (II-1-62) 45a)(Ia) and (II-1-64) 45b) (Ie) and (II-1-64) 45c) (Ig) and (II-1-64) 45d)(Ih) and (II-1-64) 45e) (Ii) and (II-1-64) 45f) (Ik) and (II-1-64) 45g)(Il) and (II-1-64) 45h) (Im) and (II-1-64) 46a) (Ia) and (II-1-65) 46b)(Ie) and (II-1-65) 46c) (Ig) and (II-1-65) 46d) (Ih) and (II-1-65) 46e)(Ii) and (II-1-65) 46i) (Ik) and (II-1-65) 46g) (Il) and (II-1-65) 46h)(Im) and (II-1-65) 47a) (Ia) and (II-1-66) 47b) (Ie) and (II-1-66) 47c)(Ig) and (II-1-66) 47d) (Ih) and (II-1-66) 47e) (Ii) and (II-1-66) 47f)(Ik) and (II-1-66) 47g) (Il) and (II-1-66) 47h) (Im) and (II-1-66) 48a)(Ia) and (II-1-67) 48b) (Ie) and (II-1-67) 48c) (Ig) and (II-1-67) 48d)(Ih) and (II-1-67) 48e) (Ii) and (II-1-67) 48f) (Ik) and (II-1-67) 48g)(Il) and (II-1-67) 48h) (Im) and (II-1-67) 49a) (Ia) and (II-1-68) 49b)(Ie) and (II-1-68) 49c) (Ig) and (II-1-68) 49d) (Ih) and (II-1-68) 49e)(Ii) and (II-1-68) 49f) (Ik) and (II-1-68) 49g) (Il) and (II-1-68) 49h)(Im) and (II-1-68) 50a) (Ia) and (II-1-69) 50b) (Ie) and (II-1-69) 50c)(Ig) and (II-1-69) 50d) (Ih) and (II-1-69) 50e) (Ii) and (II-1-69) 50f)(Ik) and (II-1-69) 50g) (Il) and (II-1-69) 50h) (Im) and (II-1-69) 51a)(Ia) and (II-1-70) 51b) (Ie) and (II-1-70) 51c) (Ig) and (II-1-70) 51d)(Ih) and (II-1-70) 51e) (Ii) and (II-1-70) 51f) (Ik) and (II-1-70) 51g)(Il) and (II-1-70) 51h) (Im) and (II-1-70) 52a) (Ia) and (II-1-71) 52b)(Ie) and (II-1-71) 52c) (Ig) and (II-1-71) 52d) (Ih) and (II-1-71) 52e)(Ii) and (II-1-71) 52f) (Ik) and (II-1-71) 52g) (Il) and (II-1-71) 52h)(Im) and (II-1-71) 53a) (Ia) and (II-1-72) 53b) (Ie) and (II-1-72) 53c)(Ig) and (II-1-72) 53d) (Ih) and (II-1-72) 53e) (Ii) and (II-1-72) 53f)(Ik) and (II-1-72) 53g) (Il) and (II-1-72) 53h) (Im) and (II-1-72)

However, the general or preferred radical definitions or illustrationslisted above can also be combined with one another as desired, i.e.between their respective ranges and preferred ranges. The definitionsapply to the end products and, correspondingly, to precursors andintermediates.

Preference according to the invention is given to active compoundcombinations comprising compounds of the formulae (I) and (II), wherethe individual radicals are a combination of the meanings listed aboveas being preferred (preferable).

Particular preference according to the invention is given to activecompound combinations comprising compounds of the formulae (I) and (II),where the individual radicals are a combination of the meanings listedabove as being particularly preferred.

Very particular preference according to the invention is given to activecompound combinations comprising compounds of the formulae (I) and (II),where the individual radicals are a combination of the meanings listedabove as being very particularly preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl,can in each case be straight-chain or branched as far as this ispossible, including in combination with heteroatoms, such as, forexample, in alkoxy.

Optionally substituted radicals can be mono- or polysubstituted, wherein the case of polysubstitution the substituents can be identical ordifferent.

In addition, the active compound combinations may also comprise furtherfungicidally, acaricidally or insecticidally active additives.

If the active compounds in the active compound combinations according tothe invention are present in certain weight ratios, the synergisticeffect is particularly pronounced. However, the weight ratios of theactive compounds in the active compound combinations can be variedwithin a relatively wide range. In general, the combinations accordingto the invention comprise active compounds of the formula (I) and themixing partner of the formula (II) in the preferred and particularlypreferred mixing ratios given:

The preferred mixing ratio is from 250:1 to 1:50.

The particularly preferred mixing ratio is from 25:1 to 1:10.

The mixing ratios are based on weight ratios. The ratio is to beunderstood as meaning active compound of the formula (I): mixing partnerof the formula (II).

The mixing ratios required for finding the synergism are not necessarilythe preferred mixing ratios relevant for 100% activity.

The active compound combinations according to the invention are suitablefor controlling animal pests, preferably arthropods and nematodes, inparticular insects and arachnids, found in agriculture, in animalhealth, in forests, in the protection of stored products and materialsand in the hygiene sector. They are active against normally sensitiveand resistant species, and against all or individual developmentalstages. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus,Scutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.,Schistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp.,Damalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella auriantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp., Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis,Ceratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp., Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The active compound combinations can be converted into the customaryformulations such as solutions, emulsions, wettable powders,suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and microencapsulations in polymericmaterials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to useorganic solvents as cosolvents. The following are essentially suitableas liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulfoxide, or else water.

Suitable solid carriers are:

-   for example ammonium salts and ground natural minerals such as    kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or    diatomaceous earth, and ground synthetic materials such as highly    disperse silica, alumina and silicates; suitable solid carriers for    granules are: for example crushed and fractionated natural rocks    such as calcite, marble, pumice, sepiolite and dolomite, or else    synthetic granules of inorganic and organic meals, and granules of    organic material such as sawdust, coconut shells, corn cobs and    tobacco stalks; suitable emulsifiers and/or foam formers are: for    example nonionic and anionic emulsifiers such as polyoxyethylene    fatty acid esters, polyoxyethylene fatty alcohol ethers, for example    alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates,    arylsulfonates, or else protein hydrolysates; suitable dispersants    are: for example lignosulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchas alizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with other activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth-regulating substances orherbicides. The insecticides include, for example, phosphates,carbamates, carboxylates, chlorinated hydrocarbons, phenylureas andsubstances produced by microorganisms, inter alia.

Mixtures with other known active compounds such as herbicides or withfertilizers and growth regulators are also possible.

When used as insecticides, the active compound combinations according tothe invention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergists. Synergists are compounds which increase theaction of the active compounds, without it being necessary for thesynergist added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and stored-product pests, the activecompound combinations are distinguished by an excellent residual actionon wood and clay as well as good stability to alkali on limedsubstrates.

The active compound combinations according to the invention are not onlyactive against plant pests, hygiene pests and stored-product pests, butalso, in the veterinary medicine sector, against animal parasites(ectoparasites) such as hard ticks, soft ticks, mange mites, harvestmites, flies (stinging and licking), parasitizing fly larvae, lice, headlice, bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattella germanica, Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compound combinations according to the invention are alsosuitable for controlling arthropods which attack agricultural livestocksuch as, for example, cattle, sheep, goats, horses, pigs, donkeys,camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey-bees,other domestic animals such as, for example, dogs, cats, caged birds,aquarium fish and so-called experimental animals such as, for example,hamsters, guinea pigs, rats and mice. By controlling these arthropods,cases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey and the like) should be diminished, so that moreeconomical and simpler animal husbandry is possible by the use of theactive compound combinations according to the invention.

The active compound combinations according to the invention are used inthe veterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration such as, for example, by injections (intramuscularly,subcutaneously, intravenously, intraperitoneally and the like),implants, by nasal administration, by dermal administration in the formof, for example, immersing or dipping, spraying, pouring-on,spotting-on, washing, dusting, and with the aid ofactive-compound-comprising molded articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

When used for cattle, poultry, domestic animals and the like, the activecompound combinations can be applied as formulations (for examplepowders, emulsions, flowables) comprising the active compounds in anamount of 1 to 80% by weight, either directly or after 100- to 10000-fold dilution, or they may be used as a chemical dip.

Moreover, it has been found that the active compound combinationsaccording to the invention show a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and withpreference, but not by way of limitation:

Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendronspec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec., Dinoderus minutus.

Dermapterans such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus, Urocerus augur.

Termites such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus.

Bristle-tails such as Lepisma saccharina.

Industrial materials in the present context are understood as meaningnon-living materials such as, preferably, polymers, adhesives, glues,paper and board, leather, wood, timber products and paints.

The material which is to be protected from insect attack is veryparticularly preferably wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention, or mixtures comprising it, are to beunderstood as meaning, for example:

-   construction timber, wooden beams, railway sleepers, bridge    components, jetties, vehicles made of wood, boxes, pallets,    containers, telephone poles, wood lagging, windows and doors made of    wood, plywood, chipboard, joinery, or timber products which quite    generally are used in house construction or building joinery.

The active compound combinations can be used as such, in the form ofconcentrates or generally customary formulations such as powders,granules, solutions, suspensions, emulsions or pastes.

The abovementioned formulations can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersant and/or binder or fixative, waterrepellant, if desired desiccants and UV stabilizers, and if desiredcolorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for protecting woodand timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of composition or concentrate employed depends on the speciesand the abundance of the insects and on the medium. The optimal quantityto be employed can be determined in each case by test series uponapplication. In general, however, it will suffice to employ 0.0001 to20% by weight, preferably 0.001 to 10% by weight, of the activecompound, based on the material to be protected.

A suitable solvent and/or diluent is an organochemical solvent orsolvent mixture and/or an oily or oil-type organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetter.

Organochemical solvents which are preferably employed are oily oroil-type solvents with an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. Such oily and oil-typesolvents which are insoluble in water and of low volatility and whichare used are suitable mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

Mineral oils with a boiling range of 170 to 220° C., white spirit with aboiling range of 170 to 220° C., spindle oil with a boiling range of 250to 350° C., petroleum and aromatics with a boiling range of 160 to 280°C., oil of turpentine, and the like are advantageously used.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablya-monochloronaphthalene, are used.

The organic oily or oil-type solvents of low volatility and with anevaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that the mixture is solubleor emulsifiable in this solvent mixture.

In a preferred embodiment, some of the organochemical solvent or solventmixture or an aliphatic polar organochemical solvent or solvent mixtureis replaced. Aliphatic organochemical solvents which contain hydroxyland/or ester and/or ether groups are preferably used, such as, forexample, glycol ethers, esters or the like.

Organochemical binders used for the purposes of the present inventionare the synthetic resins and/or binding drying oils which are known perse and which can be diluted in water and/or dissolved or dispersed oremulsified in the organochemical solvents employed, in particularbinders composed of, or comprising, an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenol resin, hydrocarbon resin such as indene/coumarone resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin employed as binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances mayalso be used as binders, in amounts of up to 10% by weight. In addition,colorants, pigments, water repellants, odor-masking agents, andinhibitors or anticorrosive agents and the like, all of which are knownper se, can be employed.

In accordance with the invention, the composition or the concentratepreferably comprises, as organochemical binders, at least one alkydresin or modified alkyd resin and/or a drying vegetable oil. Alkydresins which are preferably used in accordance with the invention arethose with an oil content of over 45% by weight, preferably 50 to 68% byweight.

Some or all of the abovementioned binder can be replaced by a fixative(mixture) or plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds, and also crystallizationor precipitation. They preferably replace 0.01 to 30% of the binder(based on 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate,phosphoric esters such as tributyl phosphate, adipic esters such asdi(2-ethylhexyl)adipate, stearates such as butyl stearate or amylstearate, oleates such as butyl oleate, glycerol ethers orhigher-molecular-weight glycol ethers, glycerol esters andp-toluenesulfonic esters.

Fixatives are based chemically on polyvinyl alkyl ethers such as, forexample, polyvinyl methyl ether, or ketones such as benzophenone andethylenebenzophenone.

Other suitable solvents or diluents are, in particular, water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective timber protection is achieved by industrial-scaleimpregnating processes, for example the vacuum, double-vacuum orpressure processes.

The active compound combinations according to the invention can equallybe employed for protecting objects which come into contact withsaltwater or brackish water, in particular hulls, screens, nets,buildings, quaysides and signaling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent stops in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., in particular fouling by sessile Entomostraka groups, which comeunder the generic term Cirripedia (cirriped crustaceans), is ofparticular importance.

Surprisingly, it has now been found that the active compoundcombinations according to the invention have an outstanding antifoulingaction.

Use of the active compound combinations according to the inventionallows the use of heavy metals such as, for example, in bis(trialkyltin)sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I)oxide, triethyltin chloride, tri-n-butyl(2-phenyl4-chlorophenoxy)tin,tributyltin oxide, molybdenum disulfide, antimony oxide, polymeric butyltitanate, phenyl (bispyridine)bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zincoxide, copper(I) ethylenebisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferable suitable components in combinations for the antifoulingcompositions according to the invention are:

-   algicides such as    2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;-   fungicides such as benzo[b]thiophenecarboxylic acid cyclohexylamide    S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynyl    butylcarbamate, tolylfluanid and azoles such as azaconazole,    cyproconazole, epoxyconazole, hexaconazole, metconazole,    propiconazole and tebuconazole;-   molluscicides such as fentin acetate, metaldehyde, methiocarb,    niclosamid, thiodicarb and trimethacarb;    or conventional antifouling active compounds such as    4,5-dichloro-2-octyl4-isothiazolin-3-one, diiodomethylparatryl    sulfone, 2-(N,N-dimethylthiocarbamoylthio)5-nitrothiazyl, potassium    salts, copper salts, sodium salts and zinc salts of 2-pyridinethiol    1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine,    2,4,5,6-tetrachloro-isophthalonitrile, tetramethylthiuram disulfide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compoundcombinations according to the invention in a concentration of 0.001 to50% by weight, in particular 0.01 to 20% by weight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumen, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in seawater. Paintsmay furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compound combinations are also suitable for controllinganimal pests, in particular insects, arachnids and mites, which arefound in enclosed spaces such as, for example, dwellings, factory halls,offices, vehicle cabins and the like. They can be employed in domesticinsecticide products for controlling these pests. They are activeagainst sensitive and resistant species and against all developmentalstages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodnius prolixus, Triatoma infestans.

They are used as aerosols, pressureless spray products, for example pumpand atomizer sprays, automatic fogging systems, foggers, foams, gels,evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

According to the invention, it is possible to treat all plants and partsof plants. Plants are to be understood here as meaning all plants andplant populations such as desired and undesired wild plants or cropplants (including naturally occurring crop plants). Crop plants can beplants which can be obtained by conventional breeding and optimizationmethods or by biotechnological and genetic engineering methods orcombinations of these methods, including the transgenic plants andincluding the plant cultivars which can or cannot be protected by plantbreeders' certificates. Parts of plants are to be understood as meaningall above-ground and below-ground parts and organs of plants, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seedsand also roots, tubers and rhizomes. Parts of plants also includeharvested plants and vegetative and generative propagation material, forexample seedlings, tubers, rhizomes, cuttings and seeds.

The treatment according to the invention of the plants and parts ofplants with the active compounds is carried out directly or by action ontheir environment, habitat or storage area according to customarytreatment methods, for example by dipping, spraying, evaporating,atomizing, broadcasting, brushing-on and, in the case of propagationmaterial, in particular in the case of seeds, furthermore by one- ormulti-layer coating.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andparts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineeringmethods, if appropriate in combination with conventional methods(Genetically Modified Organisms), and parts thereof are treated. Theterms “parts”, “parts of plants” and “plant parts” have been explainedabove.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, better quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possiblewhich exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferred and to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparts particularly advantageous usefultraits to these plants. Examples of such traits are better plant growth,increased tolerance to high or low temperatures, increased tolerance todrought or to water or soil salt content, increased floweringperformance, easier harvesting, accelerated maturation, higher harvestyields, better quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch properties are a better defense of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), corn, soya beans, potatoes, cotton, tobacco, oilseed rapeand also fruit plants (with the fruits apples, pears, citrus fruits andgrapes), and particular emphasis is given to corn, soya beans, potatoes,cotton, tobacco and oilseed rape. Traits that are particularlyemphasized are the increased defense of the plants against insects,arachnids, nematodes and slugs and snails by toxins formed in theplants, in particular those formed by the genetic material from Bacillusthuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c),CryIIA, CryIIA, CryIII2, Cry9c Cry2Ab, Cry3Bb and CryIF and alsocombinations thereof) (hereinbelow referred to as “Bt plants”). Traitsthat are also particularly emphasized are the increased defense ofplants against fungi, bacteria and viruses by Systemic AcquiredResistence (SAR), systemin, phytoalexins, elicitors, as well asresistence genes and correspondingly expressed proteins and toxins.Traits that are furthermore particularly emphasized are the increasedtolerance of the plants to certain herbicidally active compounds, forexample imidazolinones, sulfonylureas, glyphosate or phosphinotricin(for example the “PAT” gene). The genes in question which impart thedesired traits can also be present in combination with one another inthe transgenic plants. Examples of “Bt plants” which may be mentionedare corn varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplecorn, cotton, soya beans), KnockOut® (for example corn), StarLink® (forexample corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare corn varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample corn, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulfonylureas, for example corn).Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield® (for example corn). Of course, thesestatements also apply to plant cultivars having these orstill-to-be-developed genetic traits, which plants will be developedand/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the active compound mixturesaccording to the invention. The preferred ranges stated above for themixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the mixturesspecifically mentioned in the present text.

The good insecticidal and acaricidal action of the active compoundcombinations according to the invention can be seen from the exampleswhich follow. While the individual active compounds show weaknesses intheir action, the combinations show an action which exceeds a simple sumof actions.

A synergistic effect in insecticides and acaricides is always presentwhen the action of the active compound combinations exceeds the total ofthe actions of the active compounds when applied individually.

The expected action for a given combination of two active compounds canbe calculated as follows, according to S. R. Colby, Weeds 15 (1967),20-22:

If

-   X is the kill rate, expressed as a percentage of the untreated    control, when employing active compound A at an application rate of    m g/ha or in a concentration of m ppm,-   Y is the kill rate, expressed as a percentage of the untreated    control, when employing active compound B at an application rate of    n g/ha or in a concentration of n ppm and-   E is the kill rate, expressed as a percentage of the untreated    control, when employing active compounds A and B at application    rates of m and n g/ha or in a concentration of m and n ppm,

then

$E = {X + Y - \frac{X \cdot Y}{100}}$

If the actual insecticidal kill rate exceeds the calculated value, theaction of the combination is superadditive, i.e. a synergistic effect ispresent. In this case, the actually observed kill rate must exceed thevalue calculated using the above formula for the expected kill rate (E).

After the desired period of time, the kill rate is determined as apercentage. In this case, 100% means that all animals have been killed.0% means that none of the animals have been killed.

USE EXAMPLES Example A

Heliothis armigera Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the cotton boll worm (Heliothis armigera)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed. The kill rates determined are calculatedusing Colby's formula (see page 43).

In this test, the following active compound combination in accordancewith the present application showed a synergistically enhanced activitycompared to the active compounds applied on their own:

TABLE A Plant-damaging insects Heliothis armigera test Concentration ofKill rate in % active compound after 6^(d) Active compounds in ppmfound* calc.**

0.0064 0

4 40

4 0

4 25 (II-1-9) + (Im) clothianidin (1:625) 0.0064 + 4 75 40 (II-1-9) +(Ia) imidacloprid (1:625) 0.0064 + 4 75 0 (II-1-9) + (Ik) thiacloprid(1:625) 0.0064 + 4 65 25 *found = activity found **calc. = activitycalculated using Colby's formula

Example B

Myzus persicae Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by thegreen peach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed. The kill rates determined are calculated using Colby'sformula (see page 43).

In this test, for example, the following active compound combination inaccordance with the present application shows a synergistically enhancedactivity compared to the active compounds applied on their own:

TABLE B Plant-damaging insects Myzus persicae test Kill rate in %Concentration of active after 6^(d) Active compounds compound in ppmfound* calc.**

0.8 0

0.8 30 (II-1-9) + (Im) clothianidin (1:1) 0.8 + 0.8 55 30 *found =activity found **calc. = activity calculated using Colby's formula

Example C

Phaedon cochleariae Larvae Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed. The kill rates determined are calculatedusing Colby's formula (see page 43).

In this test, the following active compound combination in accordancewith the present application showed a synergistically enhanced activitycompared to the active compounds applied on their own:

TABLE C Plant-damaging insects Phaedon cochleariae larvae test Kill ratein % Concentration of active after 6^(d) Active compounds compound inppm found* calc.**

0.0064 0

4 20 (II-1-9) + (Ia) imidacloprid (1:625) 0.0064 + 4 60 20 *found =activity found **calc. = activity calculated using Colby's formula

Example D

Plutella xylostella Test (Normally Sensitive Strain)

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of caterpillars of the diamond back moth (Plutellaxylostella, normally sensitive strain) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed. The kill rates determined are calculatedusing Colby's formula (see sheet 1).

In this test, the following active compound combination in accordancewith the present application showed a synergistically enhanced activitycompared to the active compounds applied on their own:

TABLE D Plant-damaging insects Plutella xylostella test (normallysensitive strain) Kill rate in % Concentration of active after 6^(d)Active compounds compound in ppm found* calc.**

0.0064 20

4 0

4 0

4 0 (II-1-9) + (Im) clothianidin (1:625) 0.0064 + 4 100 20 (II-1-9) +(Ia) imidacloprid (1:625) 0.0064 + 4 95 20 (II-1-9) + (Ik) thiacloprid(1:625) 0.0064 + 4 40 20 *found = activity found **calc. = activitycalculated using Colby's formula

Example E

Spodoptera frugiperda Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the armyworm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed. The kill rates determined are calculatedusing Colby's formula (see page 43).

In this test, the following active compound combination in accordancewith the present application showed a synergistically enhanced activitycompared to the active compounds applied on their own:

TABLE E Plant-damaging insects Spodoptera frugiperda test Kill rate in %Concentration of active after 6^(d) Active compounds compound in ppmfound* calc.**

0.0064 0

4 0

4 0 (II-1-9) + (Ia) imidacloprid (1:625) 0.0064 + 4 20 0 (II-1-9) + (Ik)thiacloprid (1:625) 0.0064 + 4 25 0 *found = activity found **calc. =activity calculated using Colby's formula

1. A composition consisting essentially of a compound of formula (I)selected from the group consisting of

and a compound II-1-4

at a weight ratio of 25:1 to 1:10, and optionally one or more extendersor surfactants.
 2. A composition comprising a compound of formula (I)selected from the group consisting of

and a compound II-1-4

at a weight ratio of 25:1 to 1:10, and optionally one or more extendersor surfactants.
 3. A method of controlling animal pests comprisingcontacting the animal pests with a composition according to claim
 1. 4.A process for preparing pesticides, comprising mixing a compound offormula (I) as set forth in claim 1 and at least one compound of formula(II-1-4) as recited in claim 1 with extenders, surfactants, orcombinations thereof.
 5. A method of controlling animal pests comprisingcontacting the animal pests with a composition according to claim
 2. 6.A process for preparing pesticides, comprising mixing a compound offormula (I) as set forth in claim 2 and at least one compound of formula(II-1-4) as recited in claim 2 with extenders, surfactants, orcombinations thereof.